Oxyamkylateb phenol-aldehyde diols



l atentecl Mar. 7, 1950 2,499,362 FFlCE XYALKYLATED PHENQL-ALDEHYDE DIOIlS AND DERWATIVES THEREOF Melvin De Groote, University City, and Bernhard Keiser, Webster Groves, llllm, assignors to Petrolite Corporation, Ltd, Wilmington, Dell, a corporation of llllelavvare No Drawing. Application May 31, 1947, Serial No. 7531,62?

l Claims. (cl. sec-no.5)

This invention relates to new materials or new compositions of matter consisting of oxyalkylated derivatives of diphenylolmethanes prepared from certain phenols and aldehydes, to certain fractionally and totally esterified forms of such oicyalkylated derivatives, and to methods for their preparation. To come within this inventlon, a product must have the required composition and must be surface-active and hydrophile, i. e., it must be Water-soluble, water-dispersible, or self-emulsifiable. Products of the kind clisclosed and claimed herein are themselves useful in various arts. In addition, they are useful as intermediates in the preparation of other products, as will be mentioned below.

Our invention requires first the preparation of diphenylolinethanes from certain aldehydes and phenols, in the proportions and under the conditicns set out in detail below; and the subsequent oxyalkylation of such parent compounds by the use of certain oxyallrylating agents to produce a principal embodiment of our invention. Such oxyall-iylated products are contemplated for use in various arts. They are also useful as intermediates in preparing a second principal embodiment of our invention. They are further useful as intermediates in the preparation of certain derivatives not included in the present invention.

The reagents of this invention may be visualized ill as substituted rnethancs, in which two of the four methane carbon valences are satisfied by phenolic residues of specified composition; one of the two remaining positions is occupied by hydrogen;

the last position is occupied either by hydroor by a hydrocarbon radical, whether of the allryl, aryl, arallryl, acyclic, cyclic, or alicyclic type, depending upon the nature of the aldehydic reactant used. The reagents may likewise be easily visualized as consisting of two modified phenolic residues connected by a methylene or a mono-substituted methylene bridge.

In our reagents, the molecule contains two residues derived from certain til-functional monocyclic and monohydric phenols. Di-functional (iii-reactive) phenols, to be suitable as reactants here, must contain one hydrocarbon substituent in the 2,4,6 position. Such hydrocarbon subill stituent may contain either 2 or 3 carbon atoms.

Phenolic bodies are widely used in resiniflcation processes. In such reactions, the 2,4 and 6 positions oi the phenolic ring (numbering from the phenolic hydroxyl group as occupying position 1) are the reactive positions. Since these three po sitions are equivalents in such reactions, we shall refer to them herein as the 2,4,6 position, meaning that any one of them is equally intended. (it should be distinctly understood that we do not consider our reagents to be resins, however.) "Where all three such positions are oo- (is: copied by hydrogen, they are obviously all. three available in such reactions; and the phenolic termed tri-functional or tri-reactive.

'Iri-functional phenols are not usable as phenolic reactants herein. Mono-functional. phetools are likewise not included as usable reactants to produce our reagents.

The aldehydic reactant is present for the purpose of supplying the connecting bridge or link between. two molecules of the phenol. The proportion of aldehydic reactant is carefully controlled, so as to produce a maximum amount of diphenylolmethane. We have found that if one uses 1 mole of aldehyde for two moles of phenol, i. e., the theoretical proportions of reactants, the reaction is inclined to be somewhat short of complete. We have therefore found it advisable to use slightly larger than theoretical proportions of aldehydic reactant, e. g, 1.05 or possibly as much as 1.10 moles of aldehyde for 2 moles of phenol. An appreciably larger proportion of the aldehydlc reactant should not be employed, because it is conducive to the formation of molecules containing more than 2 phenolic nuclei each; and these are distinctly not included within the scope of our invention. It appears, however, that some slight excess of aldehyde, of the order stated, is

desirable. If a minor proportion of some product containing 3 phenolic nuclei in the molecule happened to be formed in the preparation of our reagent, its presence would not be detrimental to such products use in the applications stated below. Such impure or, rather, technically pure product is still to be considered as coming within our invention. The same is true if any uncombined excess of phenol happens to be present.

Use of an appreciably smaller ratio of aldehyde to phenol than 1 to 2 merely results in incomplete combination of the phenol, the amount re-' maining uncombined contributing little or nothing to the value of the product and at the same time raising its cost. Therefore, reactant proportions should be quite closely adhered to, and should be of the order of those just recited above Di-functional phenols are characterized by the 1 is para; and only positions 2 and 6 are available.

In general, para-substituted phenols are more readily procurable commercially and command lower prices than ortho isomers. For these reacide, hydroxypropyleneoxy residue sons, and also because in some instances we have is not affected by reactions of the kind just discussed above, we specifically include di-functional phenols prepared from meta-cresol or 3,5

xylenol (i. e., di-functional phenols in which either or both the 3 and the 5 positions are occupied by methyl groups) within the class of raw materials for producing our reagents.

Mixtures of the di-functional phenols named belowmay be employed to produce our reagents, instead of a single member of the specified class.

To be acceptable for use herein, a di-functional phenol must contain a substituent in the 2,4,6 position, which .substituent is a hydrocarbon radical. Such hydrocarbon radical may contain either 2 or 3 carbon atoms, e. g., it may be the ethyl, propyl, isopropyl radical, etc. It obviously must be linear rather than cyclic, because of the limited number of carbon atoms present.

The phenols used as reactants to prepare our reagents are specified to be monocyclic phenols, in the sensethat they do not contain a condensed or fused ring. The naphthols are specifically excluded from the present application. Our phenols are also required to be monohydric, i. e., they contain only one phenolic hydroxyl group per molecule.

In our products, both phenolic hydroxyl groups present in the parent diphenylolmethane, as prepared from a di-functional phenol of specified type, and an aldehyde, have been replaced, by a residue obtained from an alpha-beta low molal alkylene oxide. The alkylene oxides which we may use in preparing our reagents are limited to thosecontaining 4 carbon atoms or less. They consist of ethylene oxide, propylene oxide, butylene oxide, glycide, and methylglycide. Glycide may be considered to be hydroxypropylene oxide; and methylglycide, hydroxybutylene oxide.

,Such alkylene oxides react with various substances, including phenols, to introduce one or more divalent alkyleneoxy groups, i. e., ethyleneoxy C2H4O; propyleneoxy, -CaH60-; butyleneoxy, -C4HaO-, or generally or, .in the case of glycide and methylgly- (-C3H5(OH) O-), or hydroxybutyleneoxy (C4H1(OH)O-), into the phenol molecule. Such alkylene oxide is interposed between the phenolic hydroxyl groups oxygen atom and its hydrogen atom. The result of this reaction is to convert the phenolic hydroxyl group into a glycol or hydroxylated glycol radical, one alcoholic hydroxyl group of which has been etherified with the phenolic residue, and the other or others are free to participate in any subsequent desired reactions. Depending upon the proportion of alkylene oxide available and the conditions under which reaction is conducted, it is possible to introduce from 1 to as many as 60 or more alkyleneoxy units at each phenolic hydroxyl group, in this manner. In the present invention, we

desire to specify that from 1 to 60 such units may be present for each original phenolic hydroxyl group in our reagents, so long as they retain certain specified properties stated in detail below.

Because glycide and methylglycide are so infrequently employed, we shall confine our subsequent remarks below essentially to ethylene oxide, propylene oxide, and butylene oxide. It must be always remembered that when we speak henceforth of alkylene oxide residues, or illustrate our statements by references to one or more of the three non-hydroxylated members of our class, we nonetheless always include glycide and methylglycide as full equivalents thereof. When we refer to glycol or polyglycol radicals hereinj-it is to be understood that hydroxyglycol or hydroxypolyglycol radicals are meant if the reactant is glycide or methylglycide. Glycide is so reactive that its use is not recommended, because of the hazard involved. It. nevertheless comes within the purview of our invention. Mixtures of all our alkylene oxide reactants may be used, if desired, instead of any single one of them.

In our simpler products, then, the two phenolic hydroxyl groups of a diphenylolmethanes have been converted into two glycol or polyglycol radicals having one free alcoholic hydroxyl group (in the case of glycideand methylglycide-derived reagents, two or more) each. In our more complex reagents, such as free alcoholic groups have been esterified, e. g., with a higher fatty acid, to produce fractional or total esters. Detailed consideration of this phase of our invention is deferred momentarily.

The radical or residue which appears in our reagents as a bridge or link between the two modified phenolic radicals discussed above, is obtained from a suitable reactive aldehyde containing not more than 8 carbon atoms. Such aldehyde may be aliphatic; it may be aromatic; or it may be cyclic. The simplest aldehydic reactant is formaldehyde; and because of its wide availr ability, low cost, and high reactivity in the present invention, we name it as our generally preferred reactant of this class. If cyclic polymer, trioxane,

may sometimes be employed to advantage. Its homologues, such as acetaldehyde or its polymer paraldehyde, propionaldehyde, butyraldehyde, and heptaldehyde, are obvious equivalents. Aromatic aldehydes like benzaldehyde are usable. Furfuraldehyde, representative of the class of heterocyclic aldehydes, is usable, etc. Obviously, where a material, although an aldehyde possesses some more reactive functionality than its aldehydic character, it may not react as an aldehyde here, and hence may be unsuitable for use in preparing our reagents. Mixtures of suitable aldehydes containing less than 9 carbon atoms are usable to prepare our reagents.

To smnmarize the foregoing briefly, our reagents are prepared from diphenylolmethanes which have themselves been obtained from low molal aldehydes and certain di-functional phenols, but not from mono-functional or tri-functional phenols. If procurable commercially, such diphenylolmethanes may be purchased rather than prepared. Such diphenylolmethanes are then subjected to oxyalkylation by means of a low molal oxyalkylating agent, in which process from 1 to 60 alkyleneoxy residues are introduced at each phenolic hydroxyl group, between the oxygen and hydrogen atoms thereof. Such oxyalkylated diphenylolmethanes are themselves an importamp R; I Bri l-3 1'1. 01'

I detailed as in the second formula shown, where they are seen to consist of the radicals -R30(R4o)nR'h wherein R315 the phenolic nucleus containing a snbstituent hydrocarbon radical, as above defined; R4 is an alkylene or hydroxyalkylene radical, either C2Hii -C3Hc --C4Ha -C3I-I5(OH); or C4H-:(OH)-; n is a number between 1 and 60; and P1: is either hydrogen or the acyl radical of a high molal or a low molal monocarboxylic acid, with the limitation that at least one of the two occurrences of R1 must rep.- resent the acyl radical of a high molal monocarboxylic acid if either is acyl, as explained further below. Rs in both formulas may be either hydrogen or an organic radical containing 7 carbon atoms or less, but at least one occurrence must represent hydrogen. (Where both occurrences of R2 represent hydrogen, formaldehyde was the parent aldehydic reactant. Where benzaldehyde was the aldehyde employed, the second R2 would represent the (36155 radical. If furfuraldehyde were the aldehyde used, the second occurrence of R2 would represent the cyclic radical, Gil-I30. If acetaldehyde were used, the second Ra would represent the aliphatic radical, CH3. These examples are illustrative.)

To detail this last generic formula still further, so as to show the phenolic residue in clearer fashion, the following formula is offered:

In this formula, one occurrence of R2 represents hydrogen and the other occurrence represents either hydrogen or an organic radical, as before. R4 is an alkylene radical or radicals each containing from 2 to 4. carbon atoms (and also containing a hydroxyl group if derived from elycide or methylglycide). The n occurrences of the alkyleneoxy radical R40 number between 1 and 60, for each occurrence of 11. shown. R is a hydrocarbon radical containing either 2 or 3 carbon atoms and located in the 2,4,6 position of a parent di-functional phenol. Re is a monocyclic aromatic ring, which ma contain a methyl group in either or both the 3 and 5 positions, so long as the phenol is (ii-functional. R1 represents hydrogen oran acyl radical derived from a monobasic carboxylic acid, with the proviso that if either occurrence of R1 represents an acyl radical, at least one such acyl radical must be that of a high molal monocarboxylic acid.

The level of oxyalkylation employed to produce satisfactory reagents will depend upon a number of factors. In all cases. however, the ultimate Product must surface-activity and must be hydrophile, to come within our invention. Since ethylene oxides the greatest oxygen-to-carbon ratio of the non-hydroxyiated I alkylene oxides which are usable, it will ordinarily require iewer moles of it to produce a required level of surface-activity than it would of butylene oxide, for example. For some purposes, however, it may be desirable to employ 'butylene oxide rather than ethylene oxide, in spite of the above fact. Sometimes an intermediate product may have a somewhat unsatisfactory surface-activity; but this is immaterial so long as the ultimate product. asserted to come within our invention, has the required surface-activity.

For some purposes, such as demulsiflcation of petroleum water-in-oil emulsions, the preferred reagent usually has a relatively high degree of water-solubility. For other uses. lower levels thereof, probably more properly to be termed water-dispersibility or self-emulsiflability, may be preferable. All our reagents are hydrophile, however; and, as such, all possess either watersolubility, water-dispersibility, or self-emulsiflability in water.

The reagents exhibit great versatility and utility as one goes from minimum to maximum hydrophile characteristics in them by varying the proportion of alkylene oxide employed in their preparation. Minimum hydrophile properties may appear, for instance, when about two ethyleneoxy radicals have been introduced for each phenolic hydroxyl group originally present. Such minimum hydrophile property means that the product shows at least self-dispersibility or selfemulsiflability in distilled water at from 30 to 60 C. In concentrations between 0.5% and 5%. Such minimum dispersibility tests are preferably conducted in absence of water-insoluble solvents. Such sol or dispersion should beat least semistable, 1. e., it should persist for from 30 minutes to 2 hours without showing appreciable separation. Of course, water-insoluble solvents may be present; and if the mixture of reagent and such insoluble solvents is at least semi-stable, then, obviously, the solvent-free reagent would be even more water-dispersible.

The product may be so slowly dispersib'le, e. g., because of solid or semi-solid character, that it is difli'cult to prepare such dispersion. In such cases, mixing the product with approximately an equal proportion or less of an alcohol like methyl or ethyl alcohol, or with ethylene glycol diethylether or diethylene glycol diethylether, etc, will result in the formation of a readily dispersible material.- The amount of solvent so included in the final aqueous dispersion is insignificant, since the latter is 0.5% to 5% concentrated as to oxyalkylated diphenylolmethane.

Mere visual examination of mixtures of the reagent with water may suffice to indicate surfaceactivity, 1. e., the product produces a homogeneous mixture which foams or shows emulsifying power. All these properties are related through adsorption at the interface, for example, at the gas-liquid or the liquid-liquid interface. It desired. surface-activity may be measured in any of the quantitative methods for determining surface and interfacial tension, such as by means of a DuNouy tensiometer or a dropping pipette.

From the standpoint of surface-activity, it will be apparent that the present reagents represent a class of materials differing from each other by small increments, as the oxyalkylatlng agent and the proportions of oxyalkylating agent are varied. Employing different homologous phenolic reactants and different homologous aldehydic reactants, one is enabled to produce with nicety a product of any desired surface-activity characteristics.

As stated above, among the principal embodiments of our reagents are certain esterifled derivatives of the foregoing oxyalkylated diphenylolmethanes, which themselves constitute an other important embodiment thereof. Since the oxyalkylated diphenylolmethanes possess at least two alcoholic hydroxyl groups, they are capable of reacting with one mole of an acidic reactant to produce a fractional ester; or with two or more. moles of such acidic reactant to produce total esters. Both ester forms are included within the present invention, so long as the acidic reactants employed meet the following specifications. (For simplicity, we are proceeding hereinafter as if the oxyalkylated dlphenylolmethanes were derived from a non-hydroxylated alkylene oxide, and therefore as if such product possessed only two alcoholic hydroxyl groups. We have already specified that glycide and methlglycide are suitable oxyalkylating agents to produce our reagents. We repeat that statement now, to make it plain that in some instances our simple oxyallzyl-ated diphenylolmethane products may contain four or more rather than two alcoholic hydroxyl groups.)

The acidic reactant employed to produce such fractional or total ester may be any monobasic carboxylic acid, whether saturated or not, which has 8 carbon atoms and not more than 32. Included among such acceptable acidic reactants are the higher fatty acids, petroleum acids like the naphthenic acids and acids produced by the oxidation of petroleum wax, rosin acids like abietic acid, etc. Of all the acceptable acids of this general class, we prefer to employ the higher fatty acids containing from 8 to 32 carbon atoms. We have found the modified higher fatty acids equivalent to the fatty acids themselves. For example, the chlorinated, brominated, hydrogenated modifications may be substituted for the simple acids. Uther modifications are suitable, so long as they retain the fundamental characteristics of the fatty acids, e. g., are caeeble of forming alkali salts which are soap-like or detergent-like in character. Instead oi the the acyl chlorides or acid anhydrides may employed in the esterifica'tion reaction, just as may any other functional equivalents of the free acids. For example, low molal esters of such acids, like the methyl or ethyl esters, may be utilized to advantage in some instances. They are effective by virtue of an alcoholysis reaction in which the allryi group is displaced from the ester by the diphenyiolmethane residue, with concomitant liberation of methyl or ethyl alcohol. The use of such low molal esters is attractive, in that any excess thereof, and also the methyl and ethyl alcohol produced in such alcoholysis reaction, may be readily removed from the reaction mass by distillation.

if desired, mixed esters or" our diphenyloh -will be first considered.

8 methanes may be prepared by using different high molal monocarboxylic aclds-in the foregoing esteriilcation step. Furthermore, so long as a high molal monocarboxylic acid is employed to esterify at least one of the alcoholic hydroxyl groups of the diphenylolmethane, monocarboxyllc acids having fewer than 8 carbon atoms may be employed to esterify the remaining alcoholic hydroxyl group or groups. Acids such as acetic. hydroxyacetic, lactic, butyric, propionic, heptolc, etc., are useful, as are their chlorides, anhydrides,

and other obvious equivalents capable of supply-' ing the acyl radical required in the esteriflcation.

0f the ester forms of our reagents, we prefer those prepared from higher fatty acids having 18 carbon atoms, and particularly such higher acids as'are unsaturated. Among such fatty acids are oleic, linoleic, linolenic, and ricinolelc acids. If desired, the mixed fatty acids recovered from the splitting of any selected saponiiiable fat or oil, such as cottonseed oil, soyabean oil, corn oil, etc., may be employed as the esterifying agent. All such high molal monocarboxylic acids above recited are members of the class of detergentforming acids, because their alkali salts are soaps or soap-like products. 0-18 acids with our oxyalkylated dlphenylolmethanes are particularly desirable where our reagents are to be used as demulslfiers for resolving petroleum emulsions of the water-in-oll The ester forms of our-reagents are useful as intermediates in further reactions, so long as they retain a functional group capable of participating in such reaction. For example, the fractional esters still contain one alcoholic hydroxyl group per molecule, which is susceptible to further esteriilcation. The total esters are likewise often useful in further reactions. For example, conjugated double bonds in the fatty acid residue are reactive, the alcoholic hydroxyl group of the ricinoleic acid residue is reactive, etc.

Having described the reagents of our invention in broad outline, we propose now to consider certain aspects thereof in greater detail.

Our reagents may be prepared in any desirable manner; but ordinarily they are prepared in two or three steps. First, the diphenylolmethane is prepared; then it is oxyalkylated; and finally derivatives of such oxyalkylated products, such as the esters, are prepared from them. Manufacture of the parent diphenylolmethane It usually involves formaldehyde and a phenolic reactant of the kind described in detail above. Condensation re actions of this type are well known and do not require detailed description. We might note that if furfuraldehycle is usedas the aldehydic reactant, alkaline condensing agents or catalysts may preferably be employed; otherwise acidic catalysts are usually preferred. The condensation reactions produc diphenylolmethanes which are oily to very viscous semi solids, or even solids, in appearance.

In all cases, substantially 2 moles of phenol are combined with 1 mole of aldehydic reactant. The reactant proportions are usually preferably slightly in excess of 1 mole of aldehyde to 2 moles of phenol, in order to facilitate completion oi the reaction, as mentioned above. For example, such ratio may be 1.05 to 2 or 1.1 to 2, or possibly as great as 1.2 to 2, without departing from our invention. Increasin the aldehyde proportion unduly is to be avoided, because it Esters of unsaturated tends to give products containin more than 3 phenolic nuclei in the molecule. Increasing the phenol proportion, i. e., reducing the aldehyde proportion unduly, may result in waste of phenol in that it will remain uncombined with the aidehyde. Such excess is therefore to. be avoided. (It will probably become oxyalkyiated, however.)

Notethat, for our purpose, the resulting diphenylolmethane need be only technically pure. In other words, if it contains even as little as G or 70% of the desired diphenylolmethane, the product is frequently acceptable. The remainder, a composition not included within our invention, is usually inert rather than positively harmful. Of course, it may needlessly increase the cost of the product to have less effective or ineffective byproducts or uncomblned materials present. We naturally prefer to have the highest quality product obtainable. Excess free phenol, if volatile, may be recovered by distillation and employed to make later lots of the product, if desired.

Since the phenolic reactant is water-insoluble and frequently solid, and the preferred aldehydic reactant, formaldehyde, is usually employed as the commercial aqueous solution of 37-40% concentration, we have found it most desirable to employ, in addition to heat and vigorous agitation, a minor proportion of a wetting or emulsifying agent to promot emulslfication of the mixture. See U. S. Patent No. 2,330,217, dated September 28, 1943, to Hunn, for examples of such preferred procedure as applied to the manufacture of resins. The following examples illustrate convenient procedures for preparing the diphenylolmethanes containing two phenolic nuclei, which are the parent substances of our reagents. While our products are distinctly not resins, because the latter have different properties and commonly contain 3 or more, and usually i or 5 or more phenolic residues, the Hun procedure noted is applicable here.

Drrnsmopm'rm Example 1 Mix p-ethylphenol, 244 poundsjformaldehyde (37%), 85 pounds (molal ratio, 2 to 1.05); 4 pounds of concentrated hydrochloric acid; and 1.5 pounds of Nacconal NMF (a product of National Aniline Co.) in a vessel equipped with a reflex condenser, stirrer, thermometer, and coils. This material, as is well known, is a monoalkyl Clo-C20, principally Cir-C14) benzene monosulionic acid sodium salt. Heat to 80 C., where a mild exothermic reaction sets in, raising the temperature to 100405 C. Reflux for 1 hour; add 100 pounds of xylene as a solvent for subsequent oxyaikylation and also to facilitate removal of water from the reaction mass. Distill the water of solution and of reaction, with the xylene, using a trap arrangement which permits return of the xylene to the vessel, but removal of water as distilled. The resulting product, when solvent-free, is soft, tacky, xylene-soluble, and a clear amber color. Molecular weight determination indicates about 85-90% of our desired reagent is present in the product. The purity may 'be increase r0 about 95% by vacuum distillation.

DIPHENYLOLMETHANE Example 2 red, clear, and xylene-soluble.

gradually receding to 100-110 0. as .water is formed. Reflux for 1 hour, add 100 pounds of xylene, and then distill the water to a temperature of 150 C. This is essentially the procedure employed in U. 8. Patent No. 2,373,058. dated April 3, 1945, to Silberkraus. The resultant product resembles that of Example 1, above.

Drrnmronn'mm .Ezample 3 Use 244 pounds of p-ethylphenol; 75.6 pounds of butyraldehyde (molal ratio, 2 to 1.05); and 4 pounds of concentrated sulfuric acid. Proceed as in Example 2, above. The product is similar to those obtained in the preceding examples. When solvent-free, it is very soft-to-fluid, dark DIPHENYLOLIETHANE Example 4 Use 244 pounds of p-ethylphenolz 119.5 pounds of heptaldehyde (molal ratio, 2 to 1.05); 4 pounds of concentrated sulfuric acid; and 100 pounds of xylene. Proceed as in Example 2, above. The product. when solvent-free, is very soft-to-iluid, xylene-soluble, clear and dark red in color.

Drrnrmomsrnms Example 5 Use 272 pounds of p-isopropylphenol; 119.5 pounds of heptaldehyde (molal ratio, 2 to 11.05); 4 pounds of concentrated sulfuric acid, and 100 pounds of xylene. The aldehyde is added to the phenol and sulfuric acid, as in Example 2 above,

adding the xylene just before starting to distill the water of reaction. The reaction product is similar in properties to those of the foregoing examples, but is slightly more viscous.

mmonumrnams Example 6 Repeat Examples 1, 2 and 3, above, but substitute p-isopropylphenol for p-ethylphenol. The product is similar to those obtained in the respective foregoing examples in which p-ethyl advantage, as shown by the foregoing examples.

For example, xylene or high-boiling aromatic petroleum solvent may be included in the reaction mass to reduce its viscosity. 1 011 completion of the reaction, it facilitates removal. of the water of solution (if the aldehyde was used in aqueous solution) and the water of reaction.

' We prefer to employ such solvent at this point in the preparation of such of our reagents as are'ultimately to be used as demulsiflers, as above noted, because the finished demulsifying agent will probably be required to contain a viscosityreducing solvent anyway, if it is to be used commercially. 7

Having prepared the parent diphenylolmethane by the foregoing or other procedures-details of such preparation being well known and also being shown in the examples above, or the materials having been purchased, if obtainable-we next oxyalkylate the material.

accuses l Oxyalkylation of such diphenylolmethane, as

\ hydroxyl groups present (the first such unit above stated, results in the interposition of an alkyleneoxy group or multiples thereof between the original phenolic hydroxyl oxygen atom and its companion hydrogen atom; and the conversion oi such original phenolic hydrorwl groups into alcoholic hydroxyl groups. Because such oxyalkylation procedure introduces oxygen atoms into the molecule being treated, in the form of ether linkages, it generally confers increasing water-solubility on such molecule. Particularly, in such cases, it confers increasing watersolubility by small increments, so that substantially any desired level of water-solubility, waterdispersibility, or seli-emulsiflability may be confer-red simply by controlling the number of alkyleneoxy groups so introduced. For different purposes, it may be desired to have higher or lower levels of oxyalkylation.

For reagents which are effective as demulsitiers for crude oil emulsions of the water-in-oil type. we prefer to employ a relatively high level of oxyalkylation, and prefer to employ ethylene oxide to achieve it. In using ethylene oxide, we have found that in some cases surface-activity and self-emulsiflability begin to appear when there has been added about half as much ethylone oxide as there is diphenylolmethane present, by weight. For some purposes, where hydrophile qualities are desired, but with low water-solubility, such resultmight be achieved by using smaller proportions of ethylene oxide or by employing some higher alkylene oxide, e. on, butyiene oxide, which has a smaller oxygen-to-carbon ratio, and hence confers less water-solubility permolecule added than does ethylene oxide.

Oxyallgvlation is a well known procedure. The allrylene oxide is added, either continuously or batchwise, in gaseous or liquid form, to the lieuid or molten diphenylolmethane, at a temperature at which the allsylene oxide will be absorbed. While the reaction is an exothermic one, it is usually required to heat the parent diphenylolmethane at the beginning of the reaction, and sometimes throughout it, to temperatures generally lying between 50 and 250 C. Reaction is preferably effected in a closed vessel, capable of withstanding the pressures developed, to pre vent loss of allzylene oxide. Pressures are sometimes low. oil the order of to o. s. i. gauge; but in some instances, especially in more elohsustlve oxyalkylation, pressures oi the order of lilt p. s. i., or even Lilillll p. s. i., may he en= countered. In some instances, the reaction is so vigorous t..at cooling must he practised, or the stirring rate must he reduced, to reduce effectiyeness of contact and consequent rate of reaction.

Catalysts are preferably employed in this r action; and alkaline catalysts are more desirable than acidic catalysts. Caustic soda, alkali carllonates, alkali alcoholates like sodium methylate, alkali soaps, etc, may be so used. The amounts employed usually lie between 0.2 and by .we'uht of the diphenylolmethaiie.

In all instances the proportion of ellcylene oxide employed. is suficient to produce selE-emulsiilability of the diphenylolmethane. In the case of ethylene oxide, about 9.5 to 2 moles per mole of diphenyolmethane may he required to produce incipient water-dispersibiiity and; surface-activity. Addition of allzylene oxide may be continued to any level desired, for the units of allrylene oxide continue to interpcse themselves between the oxy gen atom and the hydrogen atom or" the tree added to each original phenolic hydroxyl group transforming it into an alcoholic hydroxyl group).

If the oxyalkylated diphenylolmethane is to be used as an intermediate in the preparation of a fractional or total ester, the influence of the esterifyln acid on the surface-activit of the resulting ester must be'considered. For instance, if one employs an oxyalkylated diphenylolmethane which is itself only marginally surfaceactive, and esterifies it with a monocarboxylic acid having, for example 18 carbon atoms. it is possible that the effect of such esterii'ylng acid will be such as to remove the resulting ester from the class of reagents acceptable incur invention, because such ester may exhibit negligible surface-activity. In another case, the intermediate oxyalkylated diphenylolmethane employed in such esteriiication ma show undesirably high and almost true water-solubility; but the effect of the high molal esterifying acid would tend to reduce the water-solubility, and the resulting ester might show more desirable surface-activity for that purpose.

One method of varying the oxyalkyiation level is to add a small proportion of alkylene oxide, substantially sufllcient to convert only one of the two phenolic hydroxyl groups to an alcoholic hydroxyl group; then to esterify this alcoholic group with the desired high molal acid; and then to revert to oxyalkylation to introduce sufflcient alkylene oxide to solubilize the fractions. ester to the desired level.

Surface-activity of the reagents of our invention is determinable quantitatively by finding the surfaceor interfacial tension of dilute aqueous dispersions, e. g., by means of a DuNouy tensiometer or dropping pipette, etc. A value considerably lower than that of the solution water should be found in dilutions of 1% and less, if the dissolved substance is surface-active. If it were truly dissolved in the water, the values would approximate that of water. Unless the reagent has been solubilized at least to the extent that a dilute aqueous dispersion, e. g., of 0.5% to 5% concentration, exhibits substantial homogeneity for periods of from 30 minutes to 2 hours, it isusually not possible to make a satlslactory measurement of its surfaceor interfacial tension. The acceptability of a reagent in our invention is determined by the fact that it has at least sumcient surface-activity to produce an aqueous dispersion of 0.5% to 5% concentration which is substantially stable or at least semi-stable for 30 minutes to 2 hours. At the lower limit of acceptability, therefore, it may be impracticable to make a quantitative measurement of such surface-activity, as just noted. in the present instance we apply the word hyclicphlle to mean products which exhibit at least such minimum surface-activity as shown by the fact that they are capable of producing,

with water, dispersions which are at least of t such minimum stability. Insufilciently solubilized reagents are consequently excluded from the scope of our invention.

As examples of methods for preparing oxyalirylatocl diphenylolmethanes or" the present class, we submit the following:

OXYALKYLATEB DIPHENYLOLMETHANE Example 1 The xylene-free product of Example 1, Diphenylolmethane, above (at least pure), 256

' i3 grams, is mixed with 100 grams xylene and grams oi sodium methylate. Ethylene oxide is added in lull-gram lots. Addition oi the first lot is fairly prompt, being accomplished in about 0.5-

hour, at maximum temperature of about C. and maximum pressure of about 65 p. s. 1. gauge. The product, a light-colored oil, forms a milky dispersion in water, in the presence oi the xylene. Addition of a second IOU-gram lot of ethylene oxide improves the stability oi the aqueous dispersion obtainable. I A third loll-gram lot of ethylene oxide is more slowly absorbed, and requires longer time and higher temperature and pressure. The dispersibilityof the product is improved. A iourthlot of 100 grams of ethylene oxide requires some-i hours to be absorbed. the maximum pressure is about 110 p. s. i. and the maximum temperature about 155 C. Dispersibility becomes quite good at this point; and is improved slightly by addition of a filth loll-gram lot of ethylene oxide under similar conditions.

Ox'ramrxmrnn Drrnxrvxaonmrrnm Example 2 The diphenyloime'thanw oi Examples 2 to 6, Dlphenylolmethane, above, are substituted in the oxyalmlation procedure recited immediately above.

Ox'rainrtarno mrnmrtommnma Example 3 The diphenylolmethanes of Examples 1 to 16. hiphenylolmethane: above, are used in the oxyalmlation proccdure'of Example 1, immediately above, except that propylene oxide or butylene oxide is used in place of ethylene oxide.

As previously stated, one of the preferred embodiments oi our reagents is the esters, both fractional and total, with high molal monocarboxyiic acids. Such esteriflcation is commonly conducted using the free high molal acid, with small proportions oi conventional esteriflcatlon catalysts, e. a aromatic sulionic acids, alkylated l4 l'xncrroim. Hmn Moms Earn or Oxrlmmam LIITHAIII Example 2 Repeat Example l, immediately above, except use 298 parts of ricinoleic acid as the esterifying 7 acid.

Fmorromx. Hrcn Mots]. Esrsa or OxYALKYLArm Drrrmmourn'manz Example 3 Repeat Examples 1 and 2, immediately above, except use 280 parts of linoleic acid or 278 parts of linolenic acid as the esterifylng acid.

FRACTIONAL Hren Mour. Es'rrs or Oxnmnsm Drrnamonuzrmnx Example 4 Repeat Examples 1 to 3, immediately preceding, except use approximately 275 parts of the mixed fatty acids derived from cocoanut oil as the esterli'ying acid.

Faacrromr. Hmn MOLAL Earns or Oxrarxmm DIPHEHYLOLHITBANE Example 5 Repeat Examples 1 to 4, immediately above, except use approximately 280 parts of soyabedn fatty acids as the esteriiying acid.

When one employs twice as many moles of high moial esterifying acid as of oxyalkylated di phenylolmethane (assuming non-hydroxylated alkylene oxides were used), in the above esterification procedure, total esters are formed. Such total esteriflcation reactions are even easier to conduct than those employed to produce fractional esters, be-

aromatic sulfonic acids, allryl phosphoric acids,

hydrogen chloride gas, etc., and heating to temperatures somewhat above iili) C. Completeness of the reaction may be followed in such cases by noting the amount of water of reaction which is distillable; or it may be followed by determining the reduction in free carboxyl group. For i'ractional esters, of course, the proportion of eaterifying acid must be limited to the molal proportion required to esterifyonly a part of the alcoholic hydroxyl groups present. It has already been stated that functional equivalents of the free high molal acids may be employed in this esteriflcation reaction.

memorial. HIGH Menu. Esrxa or Oxrarnmrrn Drrnsnnoumrnm Example 1 One mole of the oxyalkylated diphenylolmethone produced in Oxyaikylated diphenylolmethane, Examples 1 to 3, above, (at least 85% pure) is reacted with angequi-molar proportion (2 82 parts) of oleic acid, in xylene solution. After refluxing l hour, the vessel containing the mixture is fitted with s side-arm trap and is heated to distill the approximately 18 parts of water produced in the esteriflcation.

cause the presence of excess esterifying acid is not important. It may be removed at the end of the-reaction, or it may be allowed to remain in the mass, if its presence is not undesirable in the projected use of the total ester. Employment of the methyl or ethyl ester of the esterifying acid is quite practicable here. The free acids, their acyl chlorides, their anhydrides, etc., may be equally vvell employed as in the case of the preparation of the fractional esters above.

Toranlfrcn MoLA Esra-n or OXYALKYLATED Drrnsmonmzrmna Example 1 Repeat the procedure of Fractional high molal ester of oxyalkylated diphenylolmethane, Examples 1 to 5," above, except use twice as much of the fatty acid in each case. (Note that four or more times as much high molal acid as in the preceding examples would be required to produce total esters from. omalkylated diphenyloh igethanes prepared from glycide or methylglyci e.)

TOTAL HIGH Momu. Esrxa or OxYALKrLa'rnp Dmnamrnonusrnmu Example 2 following examples embody this phase oi our reagents.

Mrxzo Esrsu or Oxwuxnarnn Drrmnonmrnarm 4 Example 1 The fractional esters produced in "Fractional high molal ester of oxyalkylated diphenylolmethane, Examples 1 to 5, above, are heated with proportions of either acetic acid, hydroxyacetic acid, lactic acid, or butyric acid, sufilcient to esterii'y the remaining free alcoholic hydroxyl groups present in such fractional esters. An equivalent amount of water of esteriiication is distilled ofl, after suitable refluxing; and mixed esters of said oxyalkylated diphenylolmethanes are the resulting product.

If a total ester containing the residue of a hydroxylated monocarboxylic acid is desired,it is preferable to produce the fractional ester of any non-hydroxylated acid employed; and to use the latter in the second esteriflcation step. This avoids any possibility of reaction between the hydroxyl group of the hydroxylated acid and the carboxyl group of the other acid, in preference to reaction between the free alcoholic hydroxyl group of the oxyalkylated diphenylolmethane and the non-hydroxylated acids carboxyl group. For-example, if ricinoleic acid and a low molal non-hydroxylated acid are to be esterified, the ricinoleic acid is preferably reacted last.

In the foregoing discussion, no consideration has been given the thought that symmetrical and unsymmetrical forms of oxyalkylated diphenylolmethanes may be prepared. For example, minimum oxyalkylation may be conducted, so as to introduce a total of two moles of alkylene oxide, which convert the two phenolic hydroxyl groups to alcoholic hydroxyl groups. Then, one of the alcoholic hydroxyl groups may be blocked by reacting the partially oxyalkylated product with an acid, e. g., a high molal monocarboxylic acid, to produce a fractional ester. Such fractional ester may then be oxyalkylated further, all of the additional alkylene oxide being added at the other or free alcoholic hydroxyl group. in

such case, the esteriiied hydroxyl group position would possess only one aiiwlene oxide residue; all others introduced would be locatedat the other alcoholic hydroxyl group position.

If desired, this same procedure may be applied, but more alkylene oxide introduced in the first oxyalkylation step. In such instance, both al coholic hydroxyl groups would receive a number of allrylene oxide residues. Esteriiication at one oi such two positions would then prevent any further addition of allwlene oxide there; and any further oxyalkylation must consequently take place at the other position. This latter position would then have more ailsylene oxide residues than the fist and eats-rifled position; and the product would likewise he unsymmetrical.

Where all osyaiiwiation takes place before any esteriiication, in a single prel minary operation, distribution of alisylene oxide residues between the alcoholic hydroxyl positions will be uniform. if the two phenolic nuclei are identical; and setrical oxyalkylated esters will result on subsequent esteriflcation.

Materials of the kind herein disclosed are useful in many arts. They may be used as wetting,

detergent and levelmg agents in the laundry, textile and dyeing industries; as wetting agents and detergents in the acid-Washing of and 16 in the acid-washing of building stone and brick; as a wetting agent and spreader in the application of asphalt in road building and the like; as a constituent of soldering flux preparations; as a flotation agent in the flotation separation of various minerals; for flocculating and coagulating negatively-charged particles from various aqueous suspensions such as sewage, coal-washing waste water, various trade wastes, and the like; as germicides and insecticides; as emulsiflers for cosmetics, spray oils, water-repellent textile finishes, etc. The aforementioned uses are by no means exhaustive as to industrial uses. The most important use of our new composition of matter is as a demulsifier for dehydrating water-in-oil emulsions, and more specifically emulsions of water or brine in crude petroleum. The chemical reagents herein described are also particularly desirable for use as break inducers in the doctor treating procedure for sweetening gasoline. (See U. 8. Patent No. 2,157,223, dated May 9, 1939, to Sutton.)

Chemical compounds oi. the kind herein described are also of value as surface tension depressants in the acldization of calcareous oilbearing strata by means 01 strong mineral acid, like hydrochloric acid. As to this use, see U. S.

Patent No. 2,233,383, dated February 24, 1941, to

De Groote and Kelser. Similarly, some members are efiective as surface tension depressants or wetting agents in the working of depleted oilbearing strata by flooding, in secondary recovery operations. As to this last named use, see U. S. Patent No. 2,226,119, dated December 24, 1940, to De Groote and Keiser.

We have prepared a number of representative oxyalkylated diphenylolmethanes and esters thereof, as described herein. We have tested such representative oxyalkylated diphenylolmethane products and their esters, as herein described, and have found them to be eii'ective demulsifiers for oil-field emulsions oi the water-in-oil type. We have additionally determined that such oxyalkylated products and their esters are valuable for purposes where surface-active agents are conventionally employed. We have also determined that the oxyalkylated products and their esters herein described can be used as intermediates for the manufacture of more complicated derivatives.

While the examples show a number of representative usable phenols, it may be well to describe our preferred tri-func'tional phenolic reactants here. compositions present in or derived from the oils extracted from the anacardium genus of the anacardiaceae family. Cashew nutshell liquid is Gill ill

ascribed as consisting of about 9l% anacardic acid, (3221-13203, and 1U% caTd01 Cs2I-I52O4, with very small fractional per entages of other materials. Anacardie acid is generally accepted to be:

Pyrolytic distillation causes conversion into phenols. @ur reagents may be obtained from cashew nutshell liquid, 'anacardol (3-pentadecadienylphenoi), eardanol (dihydroanacardol or 3- pentadecenyl-phenol), and hydrogenated cardanol (dihydrocardanol or tetrahydroanacardol or 3- pentadecylphenol). Commercially, these products appear on the market in one of three forms: cardanol, treated cashew nutshell liquid, and hydrogenated cardanol.

As an example of a diphenylolmethane prepared from one such tri-iunctional phenol, and suitable for subsequent oxyalkylation, the following directions may be given: Use cardanol, 576

These are prepared from the phenolic acoasoa grams; formaldehyde (37%), 81 grams (molal ratio, 2 to 1); concentrated hydrochloric acid, 4 grams; Nacconal NRSF (a product of National Aniline Co.) 1.5 grams. Proceed as in Example 1, Diphenylolmethane, above, except that the xylene is added just before water is distilled. The product, when solvent-free, is dark red, soft or semi-fluid, and xylene-soluble.

Attention is directed to the fact that the present application is one of a series, Serial Nos. 751,600, 751,601, 751,602, 751,603, 751,604, 751,614, 751,615, 751,616, 751,618, 751,621, 751,622, 751,625, 751,626, 751,628 and 751,629, all filed of even date, and all relating to kindred subject-matter. Applications Nos. 751,614, 751,615, 751,616, 751,618, 751,621 and 751,622 are now abandoned.

Having thus described our invention, what we claim as new and desire to secure by Letters Patent is:-

1. A surface-active oxyalkylated derivative of a diphenylolmethane having the formula wherein one occurrence of R2 represents hydrogen and the other occurrence represents a member of the class consisting of hydrogen and organic radicals having 7 carbon atoms or less; R4 is a member of the class consisting of alkylene radicals and hydroxyalkylene radicals and contains 4 carbon atoms or less; Re is a monocyclic phenolic nucleus ortho-linked to the carbon atom C; R5 is a hydrocarbon radical containing from 2 to 3 carbon atoms and located in the para position of the phenolic nucleus Rs; R1 is a member of the class consisting of hydrogen, acyl radicals of monocarboxylic acids containing from 8 to 32 carbon atoms, and acyl radicals of monocarboxylic acids containing less than 8 carbon atoms, with the proviso that if either currence 01 R1 represents an acyl radical, at least one such occurrence must represent the acyl radical of a monocarboxylic acid containing from 8 to 32 carbon atoms; and n is a number between 1 and 60; with the final proviso that said derivative, in absence of water-insoluble solvents, is surface-active to the extent that it is capable of forming at least a semi-stable aqueous dispersion in 0.5% to concentration, said surfaceactivity being due to oxyalkylation in the phenolic,

hydroxyl position.

2. The product of claim 1, wherein one occurrence of R1 represents hydrogen and the other occurrence of R1 represents an aliphatic radical.

3. The product of claim 1, wherein both occurrences of R1 represent hydrogen.

4. The product of claim 1, wherein both occurrences oi R1 represent hydrogen and R; is the ethylene radical cam.

5. The product of claim 1, wherein both occurrences or R2 represent hydrogen; R4 is the ethylene radical (J-1H4; and both occurrences of 1: represent the same number.

6. The product of claim 1, wherein one occurrence of R1 represents hydrogen and the other occurrence of R1 represents the acyl radical or a monocarboxylic acid containing from 8 to 82 carbon atoms.

7. The product of claim 1, wherein one occurrence of R1 represents hydrogen; the other occurrence of R1 represents an aliphatic radical; one occurrence of R1 represents hydrogen; and the other occurrence of R1 represents the acyl radical of a monocarboxylic acid containing from 8 to 32 carbon atoms.

8. The product of claim 1, wherein both occurrences of R1 represent hydrogen; one occurrence of R1 represents hydrogen; and the other occurrence of R1 represents the acyl radical of a monocarboxylic acid containing from 8 to 32 carbon atoms.

9. The product of claim 1, wherein both occurrences of R2 represent hydrogen; R4 is the ethylene radical C2H4; one occurrence of R1 represents hydrogen; and the other occurrence of R1 represents the acyl radical of a monocarboxylic acid containing from 8 to 32 carbon atoms.

10. The product of claim 1, wherein both occurrences of R1 represent hydrogen; R1 is the ethylene radical C2H4; one occurrence of R1 represents hydrogen; the other occurrence of R1 represents the acyl radical of a monocarboxylic acid containing from 8 to 32 carbon atoms; and both occurrences of 11. represent the same number.

11. The product of claim 1, wherein one occurrence of R1 represents the acyl radical of a monocarboxylic acid containing from 8 to 32 carbon atoms, and the other occurrence of R1 represents the acyl radical of a monocarboxyllc acid containing from 1 to 32 carbon atoms.

12. The product of claim 1, wherein one occurrence of R2 represents hydrogen; the other occurrence of R2 represents an aliphatic radical; one occurrence of R1 represents the acyl radical of a monocarboxylic acid containing from 8. to 32 carbon atoms; and the. other occurrence of R1 represents the acyl radical of a monocarborwlic acid containing from 1 to 32 carbon atoms.

13. The process of claim 1, wherein both occurrences of R2 represent hydrogen; one occurrence of R1 represents the acyl radical of a monocarboxylic acid containing from 8 to 32 carbon atoms; and the other occurrence of R1 represents the acyl radical of a monocarboxylic acid containing from 1 to 32 carbon atoms.

14. The product of claim 1, wherein both occurrences oi R1 represent hydrogen; R4 is the ethylene radical C2H4; one occurrence of R1 represents the acyl radical of a monocarboxylic acid containing from 8 to 32 carbon atoms; and the other occurrence of R1 represents the acyl radical of a monocarboxylic acid containing from 1 to 32 carbon atoms.

15. The product of claim 1, wherein both occurrences or R1 represent hydrogen; R4 is the ethylene radical Cam; one occurrence of R1 represents the acyl radical of a monocarboxylic acid containing from 8 to 32 carbon atoms; the other occurrence of R1 represents the acyl radical of a monocarboxyllc acid containing from 1 to 32 carbon atoms; and both occurrences of 11. represent the same number.

mvm DE GROOTE. BERNHARD KEIBER.

' REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 1,990,985 Fonrobert et al. Feb. 12, 1935 2,330,474 De Groote Sept. 28, 1943 2,331,266 Coleman et al. Oct. 5, 1943 3,385,970 De Groote Oct. 2, 1945 

1. A SURFACE-ACTIVE OXYLKYLATED DERIVATIVE OF A DIPHENYLOLMETHANE HAVING THE FORMULA 